CN100357490C - Rare-earth transfer film method for increasing corrosion-resistance of light metal and its composite material surface - Google Patents
Rare-earth transfer film method for increasing corrosion-resistance of light metal and its composite material surface Download PDFInfo
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- CN100357490C CN100357490C CNB2005100104410A CN200510010441A CN100357490C CN 100357490 C CN100357490 C CN 100357490C CN B2005100104410 A CNB2005100104410 A CN B2005100104410A CN 200510010441 A CN200510010441 A CN 200510010441A CN 100357490 C CN100357490 C CN 100357490C
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Abstract
The present invention relates to a rare earth transfer film method for improving the surface corrosion resistance of light metal and a composite material thereof, particularly to a method for improving the surface corrosion resistance of metal and a composite material thereof. The present invention solves the problems of light metal mechanical property descending, light metal base composite material reinforcement body increase, inhomogeneous film forming and poor corrosion preventing property existing in the adoption of an anodic oxidation method, and solves the problem of environmental pollution existing in the adoption of a chemical chromate oxidation method. The method comprises the following steps: a, the surface of the light metal and/or the light metal base composite material is ground in advance; b, the material is placed in an acetone solution or an ethanol solution and ultrasonically decontaminated; c, the material is placed in an alkaline solution and deoiled; d, the material is placed in a rare earth brine solution with an added oxidizing agent, the temperature of the mixed solution is from 20 DEG C to 100 DEG C, and the material is treated for 5 to 20 minutes; e, the material is placed at the room temperature for at least 15 days or heated for 1 to 24 h at the temperature of 40 to 80 DEG C. The method is simple, and the material adopting the method has favorable corrosion preventing property.
Description
Technical field
The present invention relates to a kind of method that improves metal and composite material surface erosion resistance thereof, belong to the material surface process field, be specifically related to a kind of raising light metal and the corrosion proof rare-earth transfer film method of composite material surface thereof.
Background technology
But series of advantages such as light metal and alloy thereof have, and density is little, the conductive and heat-conductive ability is strong, the excellent and secondary processing of mechanical property have obtained using widely in national economy.Light metal-based matrix material is except the many advantages with light metal, also have outstanding advantages such as high specific tenacity, specific rigidity, wear resistance be good, thereby in fields such as space flight, aviation and automotive industry, be considered to one of the most promising new structural material.Yet the protection against corrosion problem of light metal and light metal-based matrix material fails to be well solved always.Light metal surface comes down to a surface heterogeneous owing to there are number of drawbacks such as crystal boundary, inclusion, uses the corrosion that also unavoidably causes material in complex environment.In light metal-based Composite Preparation process, introduced a large amount of enhancing bodies owing to pursuing the high mechanical property and the over-all properties of others, the existence that strengthens body causes light metal-based composite inner weave construction extremely inhomogeneous, in environment for use, very easily form corrosion cell, thereby cause its corrosion resistance relatively poor, its performance and life-span all will be seriously influenced.For a long time, people adopt anonizing and chromic salt chemistry oxidation style to carry out rotproofing to the surface of light metal and light metal-based matrix material thereof always.Adopt anonizing, can cause the light metal mechanical property to descend, and exist the enhancing body to increase for light metal-based matrix material, make that the surface conductivity of light metal-based matrix material is bad, film forming is inhomogeneous, and preservative property are poor, and increased tooling cost; Adopt chromic salt chemistry oxidation style owing to there is deleterious hexavalent chromium, harmful, also environment is polluted.From the above, two kinds of methods all can not play effective preservative activity to light metal and matrix material thereof more than.
Summary of the invention
The objective of the invention is light metal and composite material surface thereof to be carried out rotproofing for solving to have, adopt anonizing, can cause the light metal mechanical property to descend, and exist the enhancing body to increase for light metal-based matrix material, material surface electroconductibility is bad, film forming is inhomogeneous, preservative property are poor, the high problem of tooling cost and adopt chromic salt chemistry oxidation style owing to there is deleterious hexavalent chromium is to the easy a kind of raising light metal and the corrosion proof rare-earth transfer film method of composite material surface thereof that provide of the problem of polluting of environment.It may further comprise the steps: a, to light metal material or/and light metal-based composite material surface carries out pre-grinding handles, roughness is 0.01～10 μ m; B, will place acetone or alcohol solution that ultrasonic decontamination is carried out on its surface through the material that a step process is crossed to handle, the treatment time is 1～5min; C, will place basic solution to carry out oil removal treatment through the material that the b step process is crossed, solution temperature be room temperature～60 ℃, and the treatment time is 1～5min; D, will place the rare earth salt aqueous solution that is added with oxygenant through the material that oil removal treatment is crossed, the concentration of rare earth salt aqueous solution is 0.01～0.05mol/L, the add-on of oxygenant is 20～120ml/L, the temperature of mixing solutions is 20～100 ℃, treatment time is 5～20min, and the pH value of mixing solutions is 1～5; E, will at room temperature place at least 15 days or at drying baker internal heating 1～24h, Heating temperature is 40～80 ℃ through the material that the d step process is crossed.In the c step, to place NaOH solution to carry out oil removal treatment through the material that the b step process is crossed, the concentration of NaOH solution is 0.5～0.8mol/L, the pH value is 10～14, treatment time is 1～5min, and the temperature of NaOH solution is room temperature～60 ℃, in the c step, the temperature of NaOH solution is a room temperature, and the treatment time is 1min.In the d step, will place through the material that the c step process is crossed and be added with H
2O
2CeCl
3In the aqueous solution, CeCl
3The concentration of the aqueous solution is 0.02～0.05mol/L, H
2O
2Add-on be 20～120ml/L, the temperature of mixing solutions is 20～100 ℃, the treatment time is 5～20min, the pH value of mixing solutions is 1～5, in the d step, CeCl
3The concentration of the aqueous solution is 0.02mol/L, H
2O
2Add-on be 100ml/L, the temperature of mixing solutions is a room temperature, the treatment time is 10min, the pH value of mixing solutions is 2.8.It also comprises the f step: the material of crossing through the e step process is carried out follow-up sealing treatment, and the material of soon having handled is placed on and boils 2～7min in the boiling water or be 1～4% Na in weight percent concentration
3PO
4Handle 1～10min in the solution, Na
3PO
4The pH value of solution is 3～5, in the f step, the material of having handled is placed on boils 5min in the boiling water, and in the f step, it is 2.5% Na that the material of having handled is placed on weight percent concentration
3PO
4Handle 5min in the solution, Na
3PO
4The pH value of solution is 4.5.
The present invention has following beneficial effect: one, the present invention can form the top layer with excellent corrosive nature at light metal and composite material surface thereof, and this top layer and substrate combinating strength height do not come off, preservative property are good, method is simple, operation easily, and have environmental-protecting performance.Two, for determining that the surface rare earth conversion film is to the corrosion proof influence of material, galvanic corrosion behavior to differing materials before and after handling is tested, after finding that material surface covers conversion film, bigger variation has all taken place in corresponding polarization curve shape and position, the conversion film that utilizes the present invention to obtain can make the corrosion potential of light metal and matrix material thereof improve 80～200mV, and can make the difference of pitting potential and corrosion potential increase by 100～400mV, corrosion electric current density reduces by 1～2 order of magnitude.Three, adopt the present invention even at the surface conversion coating that light metal and composite material surface thereof obtain, and tooling cost being lower, is to improve light metal and the matrix material corrosion-resistant can prefered method.
Embodiment:
Embodiment one: the raising light metal of present embodiment and the corrosion proof rare-earth transfer film method of composite material surface thereof are finished by following steps: a, to light metal material or/and light metal-based composite material surface carries out pre-grinding handles, roughness is 0.01～10 μ m, and material is through deionized water rinsing; B, will place acetone or alcohol solution that ultrasonic decontamination is carried out on its surface through the material that a step process is crossed to handle, the treatment time is 1～5min, and material is through deionized water rinsing; C, will place basic solution to carry out oil removal treatment through the material that the b step process is crossed, solution temperature be room temperature～60 ℃, and the treatment time is 1～5min, and material is through deionized water rinsing; D, will place the rare earth salt aqueous solution that is added with oxygenant through the material that oil removal treatment is crossed, the concentration of rare earth salt aqueous solution is 0.01～0.05mol/L, the add-on of oxygenant is 20～120ml/L, the temperature of mixing solutions is 20～100 ℃, treatment time is 5～20min, the pH value of mixing solutions is 1～5, and material is through deionized water rinsing; E, will at room temperature place 15 days or at drying baker internal heating 1～24h, Heating temperature is 40～80 ℃ through the material that the d step process is crossed.
Embodiment two: the difference of present embodiment and embodiment one is: in a step of present embodiment, pre-grinding is carried out on 6061 aluminum matrix composite surfaces handled, roughness is 5 μ m.Adopt this method that the corrosion potential of 6061 aluminum matrix composites is improved about 150mv, the difference of pitting potential and corrosion potential increases about 300mV, and corrosion electric current density is from 6.6E-7A/cm
2Be reduced to 3.2E-8A/cm
2About.
Embodiment three: the difference of present embodiment and embodiment one is: in the c step of present embodiment, the temperature that material carries out oil removal treatment is 45 ℃, and the treatment time is 3min.Has higher antiseptic property through the material after the subsequent method step processing under this temperature.
Embodiment four: the difference of present embodiment and embodiment one is: in the c step of present embodiment, to place NaOH solution to carry out oil removal treatment through the material that the b step process is crossed, the concentration of NaOH solution is 0.5～1.5mol/L, the pH value is 10～14, treatment time is 1～5min, and the temperature of NaOH solution is room temperature～60 ℃.The conversion film that the surface of the material that adopts above-mentioned technical parameter and handled through various method steps obtains is even, and preservative property are good.
Embodiment five: the difference of present embodiment and embodiment four is: in the c step of present embodiment, the temperature of NaOH solution is a room temperature, and the treatment time is 1min.Adopt above-mentioned technical parameter in that to guarantee that material has under the prerequisite of better preservative property also cost-saved.
Embodiment six: the difference of present embodiment and embodiment one is: in the d step of present embodiment, will place through the material that the c step process is crossed and be added with H
2O
2CeCl
3In the aqueous solution, CeCl
3The concentration of the aqueous solution is 0.02～0.05mol/L, H
2O
2Add-on be 20～120ml/L, the temperature of mixing solutions is 20～100 ℃, the treatment time is 5～20min, the pH value of mixing solutions is 1～5.To place through the material that the c step process is crossed and be added with H
2O
2CeCl
3In the aqueous solution, and adopt above-mentioned technical parameter not only can make material surface and conversion film mortise, also can improve the preservative property of material.
Embodiment seven: the difference of present embodiment and embodiment six is: in the d step of present embodiment, and CeCl
3The concentration of the aqueous solution is 0.02mol/L, H
2O
2Add-on be 100ml/L, the temperature of mixing solutions is a room temperature, the treatment time is 10min, the pH value of mixing solutions is 2.8.Adopt above-mentioned technical parameter, not only can make material surface and conversion film mortise, also can improve the preservative property of material greatly.
Embodiment eight: the difference of present embodiment and embodiment one is: in the e step of present embodiment, will at room temperature place 20 days or at drying baker internal heating 20h, Heating temperature is 50 ℃ through the material that the d step process is crossed.Can guarantee material surface and conversion film mortise.
Embodiment nine: the difference of present embodiment and embodiment one is: present embodiment also increases the f step: the material of crossing through the e step process is carried out follow-up sealing treatment, and the material of soon having handled is placed on and boils 2～7min in the boiling water.The method of this sealing treatment is simple, and operation can make material surface and conversion film mortise easily, can improve the preservative property of material surface greatly, thereby prolong the work-ing life of material.
Embodiment ten: the difference of present embodiment and embodiment nine is: in the f step of present embodiment: will be placed on weight percent concentration through the material that the e step process is crossed and be 1～4% Na
3PO
4Handle 1～10min in the solution, Na
3PO
4The pH value of solution is 3～5.Through the material that this sealing treatment is crossed, can guarantee material surface and conversion film mortise more, improve the preservative property of material greatly, thereby prolonged the work-ing life of material.
Embodiment 11: the difference of present embodiment and embodiment nine is: in the f step of present embodiment, the material of having handled is placed on boils 5min in the boiling water.Adopt this method, simple, operation easily.
Embodiment 12: the difference of present embodiment and embodiment nine is: in the f step of present embodiment, it is 2.5% Na that the material of having handled is placed on weight percent concentration
3PO
4Handle 5min in the solution, Na
3PO
4The pH value of solution is 4.5.Adopt above-mentioned technical parameter can guarantee material surface and conversion film mortise more, improve the preservative property of material greatly, prolonged the work-ing life of material to greatest extent.
Embodiment 13: the difference of present embodiment and embodiment one is: in a step of present embodiment, described light metal material is aluminium or magnesium or aluminium alloy or magnesium alloy; The matrix of described light metal-based matrix material is aluminium or magnesium or aluminium alloy or magnesium alloy; Enhancing body in the described light metal-based matrix material comprises whisker, particle and fiber; Described whisker comprises borate, silicon carbide, aluminum oxide; Described particle comprises silicon carbide, aluminum oxide, titanium carbide, norbide; Described fiber comprises carbon, boron, silicon carbide, aluminum oxide, boron nitride.
Adopting above-mentioned materials, not only have wider use range, also have simultaneously and conversion film associativity preferably, is that aviation and auto industry field use more light metal material.
Claims (9)
1, a kind of raising light metal and the corrosion proof rare-earth transfer film method of composite material surface thereof is characterized in that it may further comprise the steps: a, to light metal material or/and light metal-based composite material surface carries out pre-grinding handles, roughness is 0.01～10 μ m; B, will place acetone or alcohol solution that ultrasonic decontamination is carried out on its surface through the material that a step process is crossed to handle, the treatment time is 1～5min; C, will place basic solution to carry out oil removal treatment through the material that the b step process is crossed, solution temperature be room temperature～60 ℃, and the treatment time is 1～5min; D, will place the rare earth salt aqueous solution that is added with oxygenant through the material that oil removal treatment is crossed, the concentration of rare earth salt aqueous solution is 0.01～0.05mol/L, the add-on of oxygenant is 20～120ml/L, the temperature of mixing solutions is 20～100 ℃, treatment time is 5～20min, and the pH value of mixing solutions is 1～5; E, will at room temperature place at least 15 days or at drying baker internal heating 1～24h, Heating temperature is 40～80 ℃ through the material that the d step process is crossed.
2, raising light metal according to claim 1 and the corrosion proof rare-earth transfer film method of composite material surface thereof is characterized in that last in a step, b step, c step and d step, and material is all through deionized water rinsing.
3, raising light metal according to claim 1 and the corrosion proof rare-earth transfer film method of composite material surface thereof, it is characterized in that in the c step, to place NaOH solution to carry out oil removal treatment through the material that the b step process is crossed, the concentration of NaOH solution is 0.5～0.8mol/L, the pH value is 10～14, treatment time is 1～5min, and the temperature of NaOH solution is room temperature～60 ℃.
4, raising light metal according to claim 3 and the corrosion proof rare-earth transfer film method of composite material surface thereof is characterized in that in the c step, and the temperature of NaOH solution is a room temperature, and the treatment time is 1min.
5, raising light metal according to claim 1 and the corrosion proof rare-earth transfer film method of composite material surface thereof is characterized in that in the d step, will place through the material that the c step process is crossed and be added with H
2O
2CeCl
3In the aqueous solution, CeCl
3The concentration of the aqueous solution is 0.02～0.05mol/L, H
2O
2Add-on be 20～120ml/L, the temperature of mixing solutions is 20～100 ℃, the treatment time is 5～20min, the pH value of mixing solutions is 1～5.
6, raising light metal according to claim 5 and the corrosion proof rare-earth transfer film method of composite material surface thereof is characterized in that in the d step CeCl
3The concentration of the aqueous solution is 0.02mol/L, H
2O
2Add-on be 100ml/L, the temperature of mixing solutions is a room temperature, the treatment time is 10min, the pH value of mixing solutions is 2.8.
7, raising light metal according to claim 1 and the corrosion proof rare-earth transfer film method of composite material surface thereof, it is characterized in that it also comprises the f step: the material of crossing through the e step process is carried out follow-up sealing treatment, and the material of soon having handled is placed on and boils 2～7min in the boiling water or be 1～4% Na in weight percent concentration
3PO
4Handle 1～10min in the solution, Na
3PO
4The pH value of solution is 3～5.
8, raising light metal according to claim 7 and the corrosion proof rare-earth transfer film method of composite material surface thereof is characterized in that in the f step, the material of having handled is placed on boils 5min in the boiling water.
9, raising light metal according to claim 7 and the corrosion proof rare-earth transfer film method of composite material surface thereof is characterized in that in the f step, and it is 2.5% Na that the material of having handled is placed on weight percent concentration
3PO
4Handle 5min in the solution, Na
3PO
4The pH value of solution is 4.5.
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| CN100357490C true CN100357490C (en) | 2007-12-26 |
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|---|---|---|---|---|
| CN101161869B (en) * | 2007-11-23 | 2010-06-09 | 哈尔滨工业大学 | Method for preparing rear earth corrosion resistant film on metal base composite surface |
| CN101597758B (en) * | 2009-06-26 | 2011-03-30 | 袁兴 | Low chromium anticorrosive chemical conversion treating fluid on surface of constructive aluminium profile and use method thereof |
| CN101818339B (en) * | 2010-03-30 | 2013-04-17 | 海洋王照明科技股份有限公司 | Surface rare-earth film transforming agent and surface rare-earth film transformation processing method of aluminium alloy |
| CN102080197B (en) * | 2010-12-16 | 2012-11-21 | 哈尔滨工业大学 | Method for coating surface of reinforcement in composite material |
| CN104372394A (en) * | 2014-07-03 | 2015-02-25 | 西安工业大学 | Preparation method for oxide ceramic layer |
| CN104831328A (en) * | 2015-05-28 | 2015-08-12 | 西南交通大学 | Integrated hole sealing method for anodic oxide films of aluminum alloys |
| CN106637336B (en) * | 2016-10-21 | 2018-11-30 | 重庆南涪铝业有限公司 | A kind of method for oxidation of aluminum profile |
| CN110983411A (en) * | 2020-01-07 | 2020-04-10 | 昆明理工大学 | Preparation method of natural color conversion film on surface of aluminum alloy |
| CN113430509B (en) * | 2021-06-24 | 2022-09-16 | 浙江固的管业有限公司 | Anticorrosive treatment process for stainless steel pipe fitting |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1338761A (en) * | 2000-08-11 | 2002-03-06 | 住友特殊金属株式会社 | Rareearth metal based permanent magnets with corrosionproof film and manufacture thereof |
| JP2002329629A (en) * | 2001-04-27 | 2002-11-15 | Tdk Corp | Method of manufacturing magnet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1338761A (en) * | 2000-08-11 | 2002-03-06 | 住友特殊金属株式会社 | Rareearth metal based permanent magnets with corrosionproof film and manufacture thereof |
| JP2002329629A (en) * | 2001-04-27 | 2002-11-15 | Tdk Corp | Method of manufacturing magnet |
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